CS222672B2 - Foil from partially acetalized polyvinylalcohol containing the softening agents - Google Patents

Abstract

A plasticizer-containing film of a partially acetalized polyvinyl alcohol resin contains as the plasticizer a mixture of an ester of an organic cyclic acid and/or a conventional acetal plasticizer for said resin, and an ester of an oxygen acid of phosphorus.

Description

(54) Foils of partially acetalized polyvinyl alcohols containing plasticizers

Foils of partially acetalized polyvinyl alcohols containing softening agents; as a plasticizer, a mixture of organic cyclic and / or acetal esters and phosphorous acid esters is used. The polymers of partially acetaliolated polyvinyl alcohols which are suitable for use according to the invention are used as adhesive films in laminated safety glasses and are less sensitive to the quality than the known adhesive films for laminated safety glasses, since they have a considerably lower viscosity at known discharge temperatures. foil production.

This invention relates to films of polyvinyl alcohols having a partially acetalizovených obsehiem změkfiovs ≤ t ≤ L, ^{for the} P ter ^ACTIVE DEG to use ^and as adhesive films in a paired ^{b P} ez eČnnotních glasses. More particularly, the present invention relates to novel polyvinyl butyral films and composite safety glasses made therefrom.

Associated Security! The glasses are generally composed of two plates of silicon glass and an adhesive film connecting the glass plates. Optionally, one of the silica glass plates may be provided with an artificial mortar plate. Such composite safety plates are mainly used as protective glazing for vehicles, in particular for automobile rounds; 'but they can. Even in the construction sector, depending on the application, more than two silicone or synthetic boards are adhered to the adhesive film. Such multiple plates serve oappíiled as composite bulletproof glass.

As stokers' Lie ^{tert sl} o ^: ^{i thee} c ^ ^HT rutoných. mostly softened sklec ^{h p} arciálně acetalZoovEmé film polyoioylelkbholu. The partially acetalized polyoinyl alcohols required for their preparation are prepared by saponification of polyoloyl ethyl acetate and subsequent isolation with aliphatic aldehydes, with foraaldethyde, acetaldehyde, butyradethyde and 3 to 10 aldehydes. . The liquefaction is generally not carried out completely, so that the p-lyvioyl alcohol is usually still 0.5 to 5% by weight of the ethyl group, based on the vinyl acetate groups. Also, it is usually not carried out completely, so that the partially reverse polarized vinyl alcohol used for the production of the foils usually still contains free hydroxyl groups; in the case of polyvinyl alcohol partially ecetrically bound with butyric acid (hereinafter referred to as PVB), this hydroxyl content may vary between 10 and 27%, based on vinyl alcohol. For the purposes of the present invention, all of these resins are encompassed by the term partially refractory polyvinyl alcohol.

In the manufacture of composite safety glasses, these partially refractory olefinic sulfo alcohols having a certain content of plasticizers are used as films. The type and oiooss of the used mirror is in fact! associated safety glass. In practice, it has therefore been found that in particular the net, the composite safety glass is intended to have a PVB-foil having a softening content of 15 to 39% by weight, preferably 25 to 31% by weight, and a free hydroxyl content of 10 to 25% by weight. %, preferably from 16 to 23% by weight, based on zykoocarboxylic acid-free PB-cells. The moisture content of such PVBffolie should be between 0.2 to 0.9 hyoonootic%. '

Most of the 2-methylsulphonic acid-tree-ethyl ester is used as a softening agent for such salts. The use of Ubutyto Vaccate, li- (butoxsetsl) ellipse and phthalate was described.

Requirements that are imposed on the associated safe ^! glass are very high. In ob ^ ^l as: ^{P i} te lot from - ²⁰ to ^d of +40 ° C · ^ is potočvána in FIG KLE ^{d e o} xa řilneoosSi to topLcí Limit jný ^ o ^ PR high impact strength composite safety glass plates. The film of the film must therefore have the required tensile strength and elongation at break. Of the aforementioned mirrors, the best results in this respect so far are triethyl glycerosteric acid

The 2-ytbutyric, but many of the oestos are still new:

The hitherto known partial eccentric coating of the alcoholic foil has softened and is very sensitive to moisture and absorb moisture very quickly from the eye. This causes the composite safety glasses produced therefrom to wet the edges, so that the adhesion of the foils at the edges is insufficient.

However, the disadvantage of the known adhesive films comprising the softened films is that the composite glasses produced therefrom with thicker layers of films have their own undesirable coloring.

A further disadvantage of the known partial-elastic polymers of zinc-containing resins is their high apparent osositis at extrusion temperatures. There must therefore be osteocoolos in the film at relatively high temperatures. These relatively high pressing temperatures cause high thermal stresses on the material, which it is desirable for vibrational reasons to avoid drilling processes.

The prior art adhesive films which incorporate triethylene glycol trichloro-2-butyric acid as plasticizer are not suitable for forming the bonding of the slkla with a transparent, resilient plastic, in particular polycarbonate.

SUMMARY OF THE INVENTION The object of the present invention was to provide an adhesive film for composite safety glasses based on partially acetaliolated polyvinyl alcohols containing a plasticizer having a lower moisture sensitivity than known adhesive films for composite safety glass which have a lower viscosity at extrusion temperatures. also form connections with polycarbonate and glass which nevertheless maj good elongation at break in tensile pevroosi Ar ^ ¹ ^ ZOV vroosi cold method as for Zn, ^and m ^y · c ^h EPIC Folha. .

This object has been solved by the invention of films of partially aceditized polyvinyl tetramines containing an imocobaalt, the nature of which is that the plasticizer is generally 20 to 85% by weight, preferably 30 to 50% by weight, based on the cellular weight of the film.

t.

(a) esters of organic cyclic acids, whether benzoic or phthalic, the ester components of which may be C C-^ -вО nebo nebo / and / or a ^ιι o 1Ι 1 having 1 or 2 cores, or tlglolytes, and / or themselves of known acedeles from echoquids, preferably di (frpopoQrtrytLfoгmsa.u), and

b) esters of oxygenated phosphoric acids, preferably phosphoric, phosphorous, phosphorous or phosphinic acid, the ester components of which may be the same as those mentioned in sub-paragraph a) above, one of the components of mixtures a) and b) being contained in the above plasticizer mixture in an amount at least 1% by weight, preferably at least 15% by weight, based on the abovementioned mixture.

In fóliCch invention may be such příoomno m ^ ^^ nožst and mixtures zmOkčoovαer that the Shore-A hardness moai ^p s ²³ ° ^C between ²⁰ and 90's.

The films according to the invention may preferably comprise, as esters of organic cyclic acids, in particular phthalic acid esters and, preferably, phosphoric acid esters as phosphoric acid esters.

It is well known that both phthalic acid esters and phosphoric acid esters can be used as plasticizers for partially aceditinated poly (vinyl) ethanol. The reason for their unsuccessful practical use in adhesive films for composite safe-glass glasses lies in the following facts.

For example, the phthalic acid esters can only be reacted with polyvinyl lactide in amounts up to a maximum of 20 to 25% by weight. In larger quantities, they will again calculate. However, these softeners have been found to be relatively rigid and low cold-impact strength in these relatively small amounts, making them unsuitable as adhesive films for composite safety-glass panes.

It is known that phosphoric acid esters are well tolerated with partially tetrafluorocarbon polymers. They can be added without microcrystallization up to 70% by weight. However, purely aromatic phosphoric acid esters for too low cold impact strengths and purely aliphatic phosphoric acid esters for too low tensile strength values are not in themselves suitable for the production of adhesive films for composite safety glasses. '

With comparable properties, FV-films can be compared with phosphoric acid esters as Jedi222672. With the same plasticizer, the apparent viscosity is as high as the PTEB film with triethylene glycol-2-ethyl ester as the plasticizer, so that even in this regard, the phosphoric acid esters as the sole plasticizer will not show any improvement.

However, when used as plasticizers according vjrnálezu -for ^p arciáloě acetalizovaoý polyvinylalcohol - mixed esters of phosphorus and oxygen kysedo esters of organic cyclic kyseein, which esters may, be replaced in part or wholly by conventional acetal změtečow ^ y, ^p vykaaujíVolie turn this matoeiálu lowered sensitivity to moisture,! Maai even 'j ^ s to ^p ** hmoOnootních 40% - total plasticizable ^No ooadld mectaiúctó such characteristic properties who odjpooídaáí ^Zn ° ^.gamma.CH films with 29 ^{and 30%} of the ester hnotoootnhi treeУlé01gLlčkoddip ¢ ettylmá8elné acid as umOkčooaald.

These film materials then have the desired lower apparent viscosity at extrusion temperatures. This results in the film manufacturer being able to operate at substantially lower temperatures in the extruder when the machine is heavily loaded. This makes it possible to keep the thermal load of the foil mass at a low value so that the foil of the present invention is improved. This is also manifested, for example, in the fact that the non ^- precursor glass composite made of the films according to the invention with very thick layers or multiple layers of films. шегШ inherent color, is substantially not ^from a comparable ^{and d of} the ^{Z á} en Tlelat Pirate-tálieoi ^to Torá I ^to the Ramp Cova ^{d to} lo-containing ester toietyléoglykolíi 2eetyOnáselné acid.

By means of the compositions according to the invention, it is possible to increase the number of cyclic organic acid esters in the partially acetylated polyvioyl alcohol. Thus, the isolate is only capable of being absorbed up to 20% mono -ootic with PBB. However, when 10 wt% of trioctyl phosphate is added to the PVB-resin, it is possible to add to the PVB-resin a further 25 wt% of the trioctylphosphate, until the swelling occurs. With correspondingly higher additions of trioctyiophosphate, a correspondingly higher proportion of isocisylphthalate is also possible in the plasticizer mixture, so that, for example, it is compatible with a PB-pyrosulfuric mixture of 45 wt. a total content of 85 hmoonoot% umOkčova.

Surprisingly, the compatibility of the softener compositions according to the invention with partially acetaxed is also good. polyvinylation of a low degree of acetalization. Thus, the polyvinyl alcohol components, partially acetylated butyradeelyde, containing 27% by weight of polyvinyl alcohol, can also be treated with the mixtures of plasticizers according to the invention in ools. up to 35 hoo-o-thighs without leakage, while the known umoocyald at a comparable degree of acetalization of polyvinyl alcohol butyradeehyde in these mines is already known. As expected, the foils with increasing polyvinyl alcohol content will increase in strength. Further, the tensile strength is increased by increasing the cyclic organic acid ester moieties in the plasticizer mixture, which is particularly important especially for low-poly resins.

As a result, the partially acetoisolated polyoloyl resins which may be present in the present invention may have a hydroxyl group content, calculated as the guilt of one and more, of from 5 to 30% by weight, preferably a hydroxyl group content of between 16 and 23% by weight.

Qty! The composition of the plasticizer contained in the films according to the invention may be 20 to 85% by weight, based on the total film thickness. In addition to the degree of acetalization of the polyvinyl alcohol and the aldehyde used for the detoxification, it is governed by the nature of the individual compositions used. In general, it is chosen that the Shore hardness A of the films of the present invention lies between 100 and 1 at 23 ° C.

The ratio between the esters of the phosphoric acid and the cyclic organic acid esters or acetal formers can vary between 99: 1 to 1:99. Governed largely amount and the ^ e ^ S ^ Scoil ^ c ^ o ^ s ^ ii esters of cyclic organic kyssein or acetal emollient ≤ t ≤ L, ^p arciáln ^of dcetdlUoodonéo jpolyvioy.alkotolu. He drives. le properties ^can .z volenýh jcínoO1ivýce zmokčovadel and used .parciálně acetdlUoovdméeo pol; yoioyldlčoeolj and

AND

S 222672 demands on the produced foil material. The preferred ratio is between 85:15 and 15:85% by weight. In the case of plasticizers based on esters of organic cyclic acids, acidic aromatic mono-, di- and tr- carboxylic acids, such as, for example, benzoic acid, o-, m-, p-phthalic acid and trmlliic acid, are suitable for the component. The cartoons may be substituted, inter alia, by halogen or hydroxyl groups, such as hexalhydrosalicylic acid. Also suitable as acid components are Diels-Alder adducts, for example ooleic acid or ookeinic acid anhydride with spilled diloys, and products of their hydrogenation or epoxidation, for example hexaqylro, lodotylene ether, hexa ^, trendomotylene ^, 0, 4-endooxo, 4'-hexyloxy, 4'-hexyloxy, 4'-hexyloxy, 4'-hexyloxy, 5-epoxyetrahydrophthalic acid or alpha-ethylide of the corresponding acid.

As the acid components of the phosphoric acid esters, use can be made of 5 and 3-phosphoric acids such as phosphoric acid, phosphorous acid, phosphorous acid and phosphonic acid.

The alcoholic esterification constituents of organic cyclic acids and phosphorus oxyacids are straight-chain or branched aliphatic alkyl, cleavable or C 1 -C 18 alkyl radicals which may be optionally substituted by halogen, cyclic and alkali radicals, heterocyclic radicals, preferably with one or two cores, as well as with one or two cores. For polyhydric acids, the alcohol residues may be the same or different.

Preferred ester cyclic organic cyclic acid esters are di-2-ethylhexyl phthalate, diisodeecyl phthalate, phthalates of mixtures of C 7 -C 13 alcohol-containing alcohols, benoylbutyl phthalate, dipolynyl glycol di-sloeoate, sulfonyl glycol.

Preferred phosphorous acid esters of phosphorus are t-butyloxyphenyl phosphate, 2-ethylphosphine diphosphate, diphenylphosphine.

Suitable acetal compounds which can partially or completely ester cyclic acid esters are the well-known acetals of the aliphatic or aromatic series, which are obtained from the aldehydes, preferably from 1 to 3, by weight. 3 carbon atoms, aliphatic or arallphic Ο ^ Ιιο ^. These products are also known as yo0ki: ivaaУα.

A preferred acetal emollient is di- (tolyalkynyl) film.

The films according to the invention can be prepared in a manner known per se. After mixing the constituents of the mass, the obtained foil mass is processed to the desired foils. The masses are straightforward or diffusible, casting, casting, screening, scattering, or extensible. The waste can be reprocessed in an excellent manner and formed, for example, by extruding in a film.

Foil compositions can further be used using suitable auxiliaries, such as stabilizers, enteric agents, pigments, fillers, tackifiers, and, accordingly, correspondingly, film-like films are an object of the present invention.

The composite safety glasses on which the compositions according to the invention are processed consist of at least one layer of these compositions according to the invention. They can be manufactured in a manner known per se with an unhardened, hard, straight, bent, steamed, colored, etched, structural silicate glass sheet which optionally has a wire liner. as well as with a colorless, colored, transparent, colored opaque, printed foil made in accordance with the invention having optionally inserted wires, wire meshes, fabric, or other objects. The thickness of the glass or film produced according to the invention can be varied according to the purpose and the use, as well as the number of individual layers of the composite article.

Consequently, it is possible to utilize the composite glasses which comprise the films according to the invention as adhesive films in the building sector, for doors and door systems, for windows and window systems, for parts of shops, balconies or facades, for partition walls, k department ^b al ^the ONU not ^b the payment hometown Dhu, on roofs neto roof parts, terraces, skylights or greenhouses, in telephone booths or computer devices, showcases, space cash, in prison or in rooms endangered by explosion or implosion, in each case as beztního glass to protect against puncture, breakage, shelling, fire, sound, cold, heat, heat, possibly with alarm or heating wires.

In the transport sector, the glazing of motor vehicles, rail vehicles, ships and aircraft at front, rear and side windows, doors, partitions, etc. may be considered.

phenoxy ^ ^P ro ^f olie of the invention are other ^than TAHO penetrating manner FSM them ^{d p} ro ^p drawbar with a transparent, tough-elastic umOlými materials. Especially interesting is the combination of skio / polycarbonate, which has so far been a problem due to the low odoonoosis of the polycarbonate relative to conventional PV-plasticisers. It has not been possible to conceive such an association under phthalate consumption as plasticisers in PW-films (cf. German Patent Publication No. 18 14 616). Hence, to date, special soft cast resins based on polymeric esters have been recommended for gluing polycarbonate with glass, for which a new technology had to be introduced in the glass industry. With fólšovýoi compositions of this invention naprooi that can be produced without changing the known manufacturing techiik based synergickího action ^f aaáto ^ v ^ y ^ ch and phosphate zmOkkovadel perfect laminated glass of silkááSοvéhs glass and polycarbonate in compliance with good transparency p ^ lykarbo ^ i ^ here . Film processing now needs only one type of film to produce various composite systems.

In addition to polycarbonate can be used as transparent sheets of materials also umOěých plates polyieřadkrlátu ^p oSyeřyllnOeřeetdlátu, rigid PVC, polyamide, cellulose esters, styrřn akkylositriSοvýih-polymers and others.

Examples

Ex

Into the chamber half of the alcoholic product, partially acetalisated iutyradidyl, having a hydroxyl group content of 20.7% by weight (based on ldinyldlkshoS), is admixed to the rolling mill with 25% by weight or 35% by weight of di-isobotyl phthalate. The film obtained was visually tested for swelling of the admixture and then several films were made on the cylinder layer for 48 hours. The tissue paper was loaded with no load at room temperature and 50% to 65% relative humidity, and the paper appearance was then evaluated.

Films containing 25 hmoonoot% diisoctyl phthalate showed no sweating of the plasticizer, while the foil with · 35 hmoonoot% of diisoctyl phthalate was softened.

For films containing a tonicity content of 25 tanoonoot%, the elongation at break, the tensile strength and the cold impact strength were determined. Determination of cold impact strength was performed by the VDCh 22-02 method on the test specimen arms (with S 3 according to DIN 53 504) by looking for the lowest temperature at which at least one of the six specimens bent into the lentil breaks 200 g from a drop roller falling from a height of 200 mm. The following values were obtained:

Tensile strength: 395 kp / om

Elongation at break: 218%

Cold impact strength: -30 ⁰ C.

Example 2 (Comparative example)

As in Example 1, different amounts of trioctyl phosphate or octyldiphenyl phosphate or cresyl diphenyl phosphate were mixed into a PVB resin having a hydroxyl group content of 20.7% by weight and films of 0.76 mm thickness were produced. All of the blends were softened.

Ό foils as in Example 1 were measured elongation at break, tensile strength, cold impact strength. The values obtained are shown in Table 1 below:

Table 1

Plasticizer Species % Wt. Tensile strength _o (kp / cnr) Elongation at break% Cold Impact Strength (° C) trioctyl phosphate 25 293 215 -50 trioctylphosphate 30 254 245 -50 trioctyl phosphate 50 85 483 -55 trioctyl phosphate 70 10 1 048 <-55 octyldiphenylphosphate 35 205 285 -45 octyldiphenylphosphate 50 60 538 -50 octyldiphenylphosphate 70 15 Dec 952 <-55 cresyl diphenyl phosphate 35 248 265 -25 kreyldiphenylphosphate 50 113 380 -25 cresyl diphenyl phosphate 70 41 552 -40

For comparison, a PVB film with 30% by weight of 2-ethylbutyric acid triethylene glycol ester was measured, which corresponds approximately to commercial films:

Tensile strength:

Elongation at break:

Cold impact strength:

275 kp / cm ²

297%

-50 ° C.

Commercially available PJB-resins with a hydroxyl group content of 20.7% by weight (based on vinylalkyl) were mixed on a rolling mill with various omega-di-di-phthalate (DIDP) and tritectyl phosphate (TOF). From the layers obtained on the roll, 0.76 mm thick foils were obtained, the properties of which are given in Table 2. The properties were determined as described in Examples 1 and 2.

Example 3

Table 2

Content DIDP zm0kУotadld TOF % (wt%) total wt. Tensile strength _of ^(kp / cm ²⁾ Elongation at break (%) Cold Impact Strength (° C) 22.5 7.5 30 320 245 -45 17.5 17.5 35 249 283 -50 25.0 10.0 35 260 285 -50 27.5 2,5 40 228 313 -50 30.0 15.0 45 168 322 -50 32.5 17.5 50 143 320 -55

The samples of all the films were further processed into composite non-foamed glass by placing the film between two sheets of silk-glass and heating to 130-150 ° C at a pressure of 12 bar. The obtained composite glass plate were tested for hardness mmei silkkátoýýo glass and PB-fflií aid, for instance as described in German Pat. No. 24 10 153. All of the obtained laminated glass had a Pummlwerť ^of 10.

B in no case sweat softener from foil. The range of film formulations shown in Table 2 can be described with increasing total softener content without sweating in the following form:

% hmoo. DIDP % wt. TOF % by weight, all 32.5 22.5 55 35.0 25.0 60 35.0 30.0 65 37.5 32.5 70 40.0 35.0 75 42.5 37.5 80 45.0 40.0 85

Example 4

Analogously to Example 3, PW-foils were prepared with a hydroxyl group content of 20.7% with variable contents of dioctyl phthalate (DOP) and tritktsulflate, and the mechanical values were determined. The results are shown in Table 3. In all cases, a high content of PVB-pyrazine was tolerated.

Table 3

Content DOP ŤOF (% torno.) total Tensile strength (kp / cm ² ) .Pulling break at (%) Cold Impact Strength (° C) 22.5 7.5 30 279 - 270 -45 27.5 2.5 30 332 258 -50 17.5 17.5 35 232 278 -50 30.0 5.0 35 279 285 -50 30.0 10.0 40 213 323 -50

Samples of all films were further processed into composite safety glasses by inserting the film between two sheets of silicate glass and heating to 130-150 ° C under a pressure of 12 bar. All the composite glasses obtained exhibited Pumielwert 10.

Example 5 to IQ.

Analogously to Example 3, PV films containing 20.7 wt% hydroxyl groups were prepared with a mixture of different plasticizers. The plasticizers are shown in Table 4. All plasticizer mixtures were compatible with the PVV resin. Vlastinos! the films obtained are. See Table 4.

Table 4

Example 0. 5 6 7 8 % heoOnostní 9 10 PV - essential oil 65 65 65 65 65 65 dipryl polyl-di-benzoate t 17.5 dii s ^ c ^ ee ^^^^ iftanate 7.5 17.5 17.5 17.5 ϋ- ^ ηο ^ tyl) formel 17.5 trioctyl phosphate 17.5 17.5 tributoxyethyl phosphate 17.5 octySaif enSf o sfát 17.5 eercSdefrroУ · fssfát 17.5 trans-en-S-phosphate 7.5 o tensile strength (kp / cm ^c ) 232 191 212 256 268 255 elongation at break (%) 312 308 358 284 295 265 cold impact strength (° C)  -50 -50 -50 -35 -35 -30

^Z e získanfah ^(b о1И yls further composite glass panes are made so that in each case between two kdoové silica glass plate was placed in the film at a temperature of 130 ° C and a pressure of 12 Bari association was performed. All of the films had an РшшюЪлеН. "10

In analogy to Examples 2 and 3, layers of di-di-phthalate (DIDP), optionally of diyl phthalate (DOP) and trioctylphosphate (TOF) and PVEBpryasyles with a hydroxyl group content of 20.7% by weight (based on vinyl O-alcohol) were produced on the roll. ) ·. The idle viscosity in the capillary viscometer at 483 ° K and the shear stress of 0.14 MPa (MeesaPpacaa) were measured for these rolled layers. The results are shown in Table 5.

Example 11

Table 5

DIDP Contents of DOP TOF % hmoy. total Successful viscosity Pa ^ ek p p 30.0 30 208 p 17.5 17.5 35 122 17.5 p 7.5 35 126 25.0 p 10.0 35 135 p 25.0 15.0 40 59 p 30.0 10.0 40 65 22.5 p 17.5 40 57 27.5 p 12.5 40 62

The film containing 30% mono-mono-2-ethylbutyric acid was measured at a rate of 223 Pa.sec.

Example 12

Various PVB-pyrophytes having different hydroxyl group contents (PVA content) were treated analogously to Example 3 with different amounts of dUp with dIDP and thioityl phosphate (TOF) to form foils and fixed mechanical values. The results appear from Table 6. In all cases, the high content iměěУova ^d el endured with PW-p ^ ysyřicí.

Table. 6

PVA content (% hnoU) in PVB-cup Contents im0kδovadld (% hmoo.) Tensile strength _of (kp / cm ²⁾ Elongation of break at (%) DIDP TOF total 18.4 17.5 7.5 35 153 346 25.0 10.0 35 200 312 27.5 7.5 35 223 324 30.5 10.5 40 143 385 30.0 10.0 40 159 379 22.3 7.5 17.5 35 233 262 26.8 17.5 7.5 35 256 302

These 3 PVV polystyrenes were processed in addition with 30% mono-2-methyl-2-chlorobutyric acid as a plasticizer for the films. For Vp ^ ^ y ^ ice with 26.8% content hmooaooyaími r ⁰ ly ⁱⁿ ioyldlkohllu was ijišěěnl teachings.

Example 13 ·

Analogously to Example 12 were processed further two PVEBpryslqn ^ ice content of 22.3 or 26.8% by weight of polyvinyl alcohol with 40 or 45 or 50% mixtures hmoonostními zmOkkoovadl, sesSiáva ^ ⁰ of diisodeeclftalátu (DIDP) and trooktyioosfátu (TOF ) on the films to determine compatibility with the plasticizer. The results are shown in Table 7.

Table 7

PW — ppy y lrk containing PVA (% tanoo) Content of content (% hmoo,) Interrogation DIDP TOF total 22.3 20.0 20.0. 40 No 22.5 22.5. 45 No 25.0 25.0 50 No 26.8 20.0 20.0 40 No 22.5 22.5 45 No 22.5 27.5 50 No

Example 14

Various associations have been made with the following layer structure: Silica glass (3 mm thick) and PVB-ffoie (0.38 mm thick) and transparent plastic (3 mm thick), using PVV-ffie as

(a) foil containing 30% of triethylenethoxylated 2-ethylbutyric acid as a plasticizer; and

b) a film with 35% mono-mono-lithium oleate phthalate and trooctyio phosphate (1: 1) as a grain and transparent plastic was a polycarbonate or a polyamide or a polyamide. The hardening was performed by protecting the glass cover plate on the transparent plastic side in a rubber bag which was evacuated for aeration and then placed in an autoclave at 140 ° C, 12 bar, for 1.5 hours. All film coatings containing liisolecyl phthalate and trioctyl phthalate as softening agents showed very good adhesion to the transparent plastic and were impeccable and without turbidity. After 5 m of climatic storage of 95% relative atmospheric humidity at 50 ° C, no defects occurred on these associations, even in the peripheral zones.

On the other hand, it exhibited associations with a foil which contained a diethyl ether glycolstel, only slightly adheres in the case ^of lymphelyl celeltate and, in the case of polycarbonate, a very strong turbidity. The association with polyamide had very good adhesion, was impeccable and without turbidity. In the storage test at 95% relative humidity and 50 ° C, however, after 10 days there was a disturbing turbidity due to water uptake by the PV films.

To complement these experiments, associations were made of silk glass + PW-ffUe (3 mm thick) and polycarbonate. As a PVV film, a film with 55 tanoonoot% liisoleeylphthalktj + trisktylphsfktj (ratio 1.45: 1) was directly slaughtered as a plastic film. Saružení was performed again with a cover glass plate, but without the rubber vacuum bag, and so that a packet silicate glass + PAE-ffóie + polycarbonate + a cover glass plate was stretched at ^ · · tlr.oOě AEI ^50C pair is Supposedly, ^from ovýc ^{h á} LCU and ^p ^ EREV aroben car ^for lávovacímu ^p ysclsu ^which time ^the

222672 12 film thickness was performed under conditions of 120 ° C, 12 bar and for 45 minutes. The association was absolutely impeccable.

Claims (3)

SUBJECT OF THE INVENTION CLAIMS 1. A film of partially acetalized polyvinyl alcohols comprising a grain comprising: a. 20 to 85%, preferably 30 to 50% by weight, based on the total film's moisture content, (a) esters of organic cyclic acids, whether benzoic or phthalic, the ester components of which may be C 1 -C 2 -alkyls and / or aromatic radicals having 1 or 2 nuclei, or alkenylglycolates, and / or acetal compounds known per se and preferably (e) (phenthoxyethyl) OomdLu, and b) esters of phosphoric acid, preferably phosphorous, phosphorous, phosphonous, phosphonic or phosphinic acid, the ester components of which may be the same as those mentioned in sub-paragraph a), one of which is present in the abovementioned grain mixture in an amount of at least 1 % by weight, preferably at least 15% by weight, based on the abovementioned plasticizer mixture. 2. The film according to claim 1, characterized in that there is directly such a mixture in the composition that it has a Shore hardness A at 23 [deg.] C. of between 20 and 90. 3. A film according to any one of Claims 1 to 3, characterized in that it comprises, as esters of organic cyclic k / s; ^'are alkyl esters einy ftaoové and like esters Kyas-íkatých kysein phosphorus acid esters.